Azo compounds and fiber dyed therewith



textile materials, made of or containing an ort will be understood that alkyl, as used hereganic derivative of cellulose. It is, accordingly, in, unless otherwise stated, includes. not only unan object of our invention to provide a new class substituted alkyl groups such as a methyl group, of azo dyes suitable for the dyeing or coloration an ethyl group or a propyl group but also subof organic derivatives of cellulose. Another obstituted alkyl groups such as p-hydroxyethyl, fiject is to provide a process for the coloration hydroxypro'pyl, p,'y-hydroxypropyl, e-methoxy- 20 Patented July 2,1940 0 i v i I i I AZO COMPOUNDS AND FIBER DYE!) THEREWITH James G. McNally and Joseph B. Dickey, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application February 23, 1939, Serial No. 258,020

11 Claims. (Cl. 260-205) This inventionrelates to the art of dyeing or carbon atoms, "R2 and R3 each represents an coloring. More particularly it relates to azo dye alkyl group and wherein the compounds and the application of the nuclear non-sulfonated azo dye compounds for the colv 5 oration of organic derivatives ofcellulose, parg 5 ticularly textile materials made of or containing an organic derivative of cellulose, by dyeing, grouping is in ortho or para position to the azo printing, stenciling or like methods. bond. The phenylene nucleus, R1, may be un- Organic derivatives of cellulose are charactersubstituted or substituted. It may be substi- 10 ized, by an indifferent affinity for the usual cottuted, for example, with an alkyl group, an al- 10 ton and wool dyes especially the ordinary water koxy group, a nitro group or a halogen atom. soluble dyes. Because of this, it has beenneces- Ordinarily X will be a saturated straight chain sary to develop new dye compounds suitable for hydrocarbon radicle not containing more than 4 the dyeing or coloration of materials, such as carbon atoms.

of organic derivatives of cellulose in which the ethyl or s-ethoxyethyl, for example. Similarly, I dye or dyes are applied directly from. an aqueous alkoxy, as used herein, includes groups such as suspension to the material undergoing coloraa methoxy group, an ethoxy group, a propoxy tion. A further object is to P d e dy gs n group, B-methoxyethoxy and fi-ethoxyethoxy, for

- organic derivatives of cellulose which are of good example. Illustrative of halogen may be men- 25 fastness to light and washing. Other objects will ti d br in hlorin and iodi hereinafter appear. The azo dye compounds of our invention can Typical organic derivatives of cellulose include be prepared by diazotizing a primary aromatic the hydrolyzed as well as the unhydrolyzed celluamine havi g the general formula;

39 lose organic acid esters such as cellulose acetate, j '30 cellulose formate, cellulose propionate, or cellulose butyrate and the hydrolyzed as well as the a 1 unhydrolyzed mixed organic acid esters of cellu- I R: lose such as cellulose acetate-propionate, cellulose wherein R1, R2,'R3 and X have the meaning pre- 5 acetate-butyrate, and the cellulose ethers such v'icusly assigned to them and coupling the diaas methyl cellulose, ethyl cellulose, or benzyl cel- 'zonium compound obtained with an aryl, hydrolulose. While our-"invention will be illustrated aromatic or heterocyclic coupling component. more p rly in connection with the colora- As previously indicated, the nuclear non-sultion of cellulose acetate, 2. material to which the fonated azo dye compounds of our invention can.

0 invention is especially adapted, it will be understitute valuable dyes for the coloration of organic 40 Stood t t t pp to h coloration of other derivatives of cellulose, such as those hereinbe- Organic derivatives of cellulose such as those jus fore mentioned, yielding various shades thereon mentioned. of good fastness to light-and washing. These nu:

The azo dy ccmpounds of r invention have clear non-sulfonated dye compounds likewise posthe general formular sess application for the dyeing of wool and silk 45 R: and yield generally similar shades on these ma terials as on organic derivatives of cellulose. R"N=N R(IJTXN\ Azo compounds having the above general for- R3 mula "containing a nuclear sulfonic acid group wherein R represents the residue of an aryl coucan likewise be p p d n known fashionn h v pling component of the benzene or naphthalene compounds may be prepared by sulfonationpf series, a hydroaromatic coupling component or the unsulfonated azo dye compound or by .prior a heterocyclic coupling component, R1 represents sulfonation of the intermediatesemployad. These 3., phenylene nucleus, X represents a saturated nuclear sulfonated compounds possess little or no v hydrocarbon radicle not containing more than 4 utility for the coloration of orgamc derivatives 55 of cellulose but can be employed to color textile materials such as wool and silk yielding generally similar shades as the corresponding nonsulfonated compounds. Accordingly, when the azo compounds of our invention are to be employed for the dyeing of organic derivatives of cellulose, they should not contain a nuclear sulfonic acid group. Again it is generally advantageous, when they are to be used for this purpose, that they do not containa carboxylic acid group.

The following examples illustrate the preparation of the azo dye compounds of our invention:

Example 1.

0.1 gram mole of pamino- -dimethylaminoacetophenone is dissolved iii-200cc. of water containing 35 cc. of 36% hydrochloric acid; The resulting solution is cooled to a temperature approximating 0-5 C. and diazotized while maintaining this temperature by the addition, with stirring, of a concentrated-aqueous solution of 6.9 grams of sodium nitrite.

12.5 grams of 5-methyl-.lfiecyclohexadione are dissolved in 200 cc. of water containing 31.8 grams of sodium carbonate. The resulting solution is cooled to a temperature approximating 010 C. by the addition of ice, for example, and the diazo solution prepared as described above is added with stirring. The coupling reaction which takes place is carried out while maintaining a temperature of about 0-10" C. Upon completion of the coupling reaction, the mixture is made slightly acid to litmus by the addition of acetic or hydrochloric acid, for example, and the dye compound is recovered by filtration, washed with water and dried. The dye compound obtained has the formula:

and colors cellulose acetate silk a; greenish yellow shade of excellent light fastness from' an aqueous suspension.

20.4 grams of p-aminoew-diethylaminoacetophenone may be substituted for the p-amino-w-dimethylaminoacetophenone of the example to obtain a dye compound which similarly colors cellulose acetate silk a greenish yellow shade of good light fastness.

Example 2 12.8 grams of barbituric acid are dissolved in 200 cc. of water containing 31 grams of sodium carbonate. The resulting solution is cooled to a temperature approximating 0-10 C. and coupled while maintaining this temperature with the diazo solution prepared in Example 1. The dye compound formed by the coupling reaction is precipitated by making the mixture slightly acid to litmus with acetic acid following which it is recovered by filtration, washed with water and dried. The dye compound obtained has the formula:

Example 3 22.3 grams of 2-amino-5-nitro-w-dimethylaminoacetophenone are diazotized in nitrosyl sulfuric acid in known manner and the diazonium compound obtained is added to an iced hydrochloric acid solution of glyceryl cresidine. The coupling reaction which takes place is completed in known manner and the dye compound formed is worked up in the usual fashion. The dye compound obtained has the formula:

CH /N0z I CH C OCH: MQ H on. o

N=NUN CHaCHOHCHnOH and colors cellulose acetate silk violet shades from an aqueous suspension.

.1 gram mole of 2-amino-5-methyl-w-diethylaminoacetophenone can be substituted for the 2- arnino-5-nitro-w-dimethylaminoacetophenone of the example to obtain a dye compound which colors cellulose acetate silk a violet shade.

Example 4 17.5 grams of ethyl-,8-hydroxyethylanillne are dissolved in cc. of glacial acetic acid and the resulting solution is cooled by the addition of ice, for example, to a temperature approximating 0-10" C. To the solution thus prepared, the diazo solution prepared as described in Example 1 is slowly added with stirring and following its addi tion the mixture is made neutral to Congo red paper with sodium acetate. Upon completion of the coupling reaction which takes place, the dye compound formed is precipitated by the addition of water, recovered by filtration, washed with Water and dried. The dye compound obtained colors cellulose acetate silk an orange shade of good light fastness.

.1 gram mole of or .1 gram mole of can be diazotized and coupled with the ethyl-,3-

hydroxyethylaniline of the example to obtain dye compounds which similarly color cellulose acetate silk orange shades of good light fastness.

The following tabulation further illustrates the compounds included within the scope of our invention together with the color they produce on cellulose acetate silk. The compounds indicated below may be prepared by diazotizing the amines listed under the heading Amine and coupling the diazonium compounds obtained with the compound specified in the column entitled Coupling 1 Compounds having the formula:

wherein R1, R2, R3 and X have the meaning previously assigned to them from which the amines used in the preparation of the azo dye compounds 1.

of our invention can be prepared, ,,as indicated above, may be prepared as describedln the literature.

The azo dye compounds of our invention are, for the most part, relatively insoluble in' water.

Those compounds which are insoluble in water may be advantageously employed for the direct dyeing of textile materials by grinding the dye to a fine powder, intimately mixing it with a suitable dispersing or solubilizing agent, and adding the resulting mixture to water or a dilute solution of soap in water to form an aqueous dyebath,

Following this known preparation of the dyebath, the textile materials to be dyed may be added g to the dyebath and the dyeing operation conducted in known fashion. -The dye compounds of our invention which are Water soluble do not, of

course, require the use of a dispersing or solubilizing agent but may be applied to silk, wool and (depending uponthe nature and position of the water-solubilizing group) organic derivatives of cellulose textile materials from an aqueous solution of the dye.lwhich may contain salt: Flor-Han:

more complete description as to how the azo dye compounds of our invention may be employed in dyeing or coloring operations, reference may be had to our U. S. Letters Patent No. 2,115,030, issued April 26, 1938. For a more detailed description as vto how the water soluble azo. dyes of our invention may be employed for the coloration of textile materials made of or containing organic derivatives of cellulose, silk and wool or mixtures of these, reference may be had to our U. S. Letters ,Ratent ary 8, 1938. We claim: 1. An azo formula:

-R-N=N-RI-fi-XN wherein R represents the residue of a coupling component selected from the grodpconsisting' a benzene, a naphthalene, a hydroaromatic and a heterocyclic coupling component, R represents a phenylene nucleus, X represents =-asaturated a.

hydrocarbon radical not containing more than four carbon atoms, R2 and R3 each represents an alkyl group. and wherein the No. 2,107,898, issuedfil ebruformula:

dye compound having the general an alk'yligroup, n-represents :1, 2, 3" or 4- and wherein the Q i I /BI $}-(CH2),.-N\ I O R: grouping in ortho or para position to the azo bond.

3. An azo dye compound having the general formula:

/Rz R-N=NR1O(CHz),.N

ll 0 Ba wherein R represents the residue of a benzene coupling component, R1 represents a phenylene nucleus, R2 and R3 each represents an alkyl group, n represents 1, 2, 3 or 4 and wherein the grouping is in the para position to the, azo bond.

4.. An azo dye compound having the general formula: f

RN=N-R1- H2) O R8 wherein R represents the residue of,a..b.enzene coupling component R -represents ,a phenylene nucleus, R2 and R3 each represents an alkyl group, n represents 1, 2, 3 or 4 and wherein the /'R2 -coH1).N

grouping is in the ortho position to the, azo bond,

5. An azo dye compound having the general m R-N ii a1c-XN wherein R represents the residue of a benzene u-flcoupling' component, R1 represents a phenylene nucleus, X represents a saturated hydrocarbon radical not containing" more than four carbon *atoms, R: and R3 each represents an alkyl group and wherein the R2 -CX-N/ grohping is in ortho or para position to the azo bond.

6. Material made of or-containing an organic *derivative of cellulose and in which said organic derivative of cellulose is colored with a nuclear non-sulfonated azo dye compound having the general formula:

wherein R represents the residue of a coupling component selected from the group consisting of a benzene, a naphthalene, a hydroaromatic and aheterocyclic coupling component, R1 represents a phenylene nucleus, X represents a saturated hydrocarbon radical not containingmore than four carbon atoms, R2 and R3 each represents an alkyl group and wherein the wherein R represents the residue of a benzene coupling component, R1 represents a phenylene nucleus, X represents a saturated hydrocarbon radical not containing more than four carbon atoms, R: and R3 each represents an alkyl group and wherein the /R2 t* I R3 grouping is in ortho or para position to the azo bond.

8. A cellulose acetate colored with a nuclear non-sulfonated azo .dye compound having the general formula:

grouping is in ortho or para position to the azo bond.

9. A cellulose acetate colored-with a nuclear non-sulfonated azo dye compound having the general formula:

a RN=NRiICXN wherein R represents the residue of a benzene coupling component, R1 represents a phenylenenucleus, X represents a saturated hydrocarbon radical not containing more than four carbon atoms, Bi and R3 each represents an alkyl group and wherein the grouping is in ortho or para position to the azo bond.

10. A cellulose acetate colored with a nuclear non-sulfonated azo dye compound having the general formula:

R2 RN=NR;-C( 0 11;) ,.N ll

wherein R represents the residue of a benzene coupling component, R1 represents a phenylene nucleus, R2 and Re each represents an alkyl group, n represents 1, 2, 3 or 4 and wherein the 'C'-(CH2)1r-N grouping is in the para position to the azo bond.

11. A cellulose acetate colored with a nuclear non-sulfonated azo dye compound having the general formula:

R2 R-N==NR1C(CH2) ,.N

wherein R represents the residue of a benzene coupling component, R1 represents a. phenylene nucleus, R2 and Rs each represents an alkyl group, n represents 1, 2, 3 or 4 and wherein the C- CH2)nN grouping is in the ortho position to the azo bond.

JAMES G. MCNAILY. JOSEPH B. DICKEY. 

